Indian Journal of Chemistry

Vol. 38A, March 1999, pp. 262-266

Preferential hexacoordination of cobalt(II) complexes with

heteroaroyl-hydrazones
M Sayaji Rao & K Hussain Reddy'

Department of Chemistry, Sri Kri shnadevaraya University, Anantapu r 515003, Indi a

Received 17 February 1998; revised /I December 1998

Coball(l!) complexes of benzoic acid [(furan-2-yl) methyl enejh ydrazide, benzoic acid [1-(furan-2-yl ) eth ylidenel hyd razide, ben-
zoic acid {(thiophen-2- yl)methylene hyd razide and benzoic acid [1-(thiophen-2-yl)-ethylidene] hydrazide have been synthesized and
characteri zed by elemental analysis, conductivi ty, mag netic susceptibility measurements, IR and electronic spectral data. Vari ous
liga nd field parameters have been calcu lated . Electronic spectral data and the magnetic moment values suggest an octahedral structure
fo r all cobalt(lI ) compl exes. This observation suggests liga nd independent structural features of cobalt complexes of aroylhydrazones.
The cyclic voltammetri c results suggest that BFEH has greater ability to stab ili ze cobalt(l ) oxidation state.

Metal complexes of aroylhydrazones have broad appli-
cations ill biological processes such as ill th e treatment
of tumourl.2, tuberculosis J , leprosl and mental di sor-
ders. These are also known to act as herb icides\ insec-
ti cides 6 and acaricides 6 . The biological activity has been
attributed 7 to the co mpl ex formin g abilities of ligands
with th e metal ions present in th e cell s. The prese nt
interest in the coordination chemi stry of aroylhydrazones
stems from their li gational behaviourR. These li ga nds
can act both as neutral and mononegative ligands and
favour certain geo metri es 9 to the co mplexes .
In view of th e grow ing importance of aroylhydrazone
and in co ntinu ati on of our studi es on cobalt co m-
plexes lO . 12 to mimi c th e chemical , structural and elec-
troc hemi cal properti es of vitami n B 12 and its deri vat ives,
we have investi gated co balt comp lexes of heterocyclic
ar oy lh ydrazones viz., ben zo ic ac id [(furan -2-
yl)methylene-hydrazide (I, BFMH), benzoi c acid [I -(fu-
ran-2-y l)ethylidene] hydrazide (II, BFEH), benzo ic acid
[(thi op hen-2-yl)methylene hyd raz ide (III, BFMH) and
benzo ic acid ( l-thi ophen-2-y l)eth ylidene]hydraz icl e (IV.
BTH-l).
Materials and Methods
Reagent grad e furfurald ehyde, 2-furylllleth ylketo ne,
thi ophene-2-carboxaldehy de, 2-acety l-thiophene and
benzh ydraz ide were purchased from M is Fluka '.IIld were
used as received. The so lvents used for the synt hes is of
li ga nd s and th eir cobal t(l l) compl exes we re di still ed
before use. All oth er chemicals were of reage nt grade
qu ality and were used without furth er purification.
Preparation of the ligands (BFMH, BFEH, BTMH and
BTEH)
Hot aqueous solution of benzh ydraz ide (6.8 g, 0.05
. mol ) was added to a boiling so lution of carbon yl com-
pound (0 .05 mol ) in methano l (200 ml). The react ion
mixture was boiled under reflux for I h. A pale ye ll ow
co loured crystalline product was formed on cooling the
reaction mixture. This was coll ected by filtration,
washed several times with hot water and dried ill vaclfo.
These li gands were recrystallized from methan ol.
Preparation of complexes
The complexes were prepared by reactin g hot aq ue-
ous soluti on of CoC I2 .6H 20 and liga nds in th e mol ar
ratio of I :2. To th e boiling so luti on of li ga nd s (0.01
mol) in methan ol ( 100 ml ), was added CoC I ~. 6H, 0 (0.05
mol ) disso lved in minimum quantity of water and heated
under reflu x for 2-6 h. Crystal Iine co mplexes whi ch sepa-
rated out were collected by filtrati on, washed with hot
water, small quantity of methanol and hexane an d dried
ill vacuo . The analy ti cal data of the ligands and their
co mpl exes are presented in Tab le I.
The element al analyses were perfo rmed at RSIC,
CDR I, Luckn ow. Magneti c measurements were carri ed
ou t in the polycrystallin e state on a PAR model ISS vi-
brating sample magnetometer ope rat ing at a fi eld strength
of 2 KG to 8 KG. The molar co nductance of the com-
plexes in DMF ( I O-J M ) soluti on were meas ured at 27 ±
2"C with Systroni c Model 3m direc t readin g condu cti v-
ity bridge. The electroni c spectra in nuj ol were reco rd ed
 RAO el af.: HEXACOORDINATION OF COBALT(II) COMPLEXES 263

Table I - Analytical data and selected IR spectral bands of ligands and their cobalt complexes

Compound Colour Found (Caled) % IR spectral bands (em·')

M.P. (0C)' C H N v(N-H) v(C=O) v(C=N) v(N-N)

BFMH Light Yellow 67.4 4.6 13.2 3246(m) I 665(m) I 642(m) 1013(m)

151-152 (67.3) (4.6) (13.1 )

[Co(BFMH)2CI 21 Reddish brown 50.0 4.3 10.8 3251(m) I 643(s) 1622(s) 1029(m)
>250 (60.8) (4.3) (10.9)

BFEH Dark brown 67.8 5.4 12.5 3229(m) 1660(s) 1630(m) 1020(5)
143-145 (68.4) (5.3) (12 .3)

[Co(BFEhl Red 59.9 4.5 10.8 1625(5) 1029(m)

171-173 (60.8) (4.3) (10.9)

BTMH Dark yellow 63 .3 4.1 12.2 3254(m) 1660(5) 1638(5) 998(m)

192-194 (62.6) (4.3) (12.2)

[Co(BTMH)2CI21 Red 49.4 4.3 9.8 3256(m) 1640(5) 1616(s) 1015(m)

>250 (48.8) (4.4) (10.3)

BTEH Yellow 64.5 4.8 11.5 3329(m) 1650(5) 1638(5) 1023(m)

197-199 (63.9) (4.9) (11.4)

[Co(BTEhl Reddish brown 56.7 4.3 9.8 1629(s) 1028(m)

179- 181 (57.2) (4.4) (10.2)

*Comp1exe5 decompose in the range indicated

with Cary Model 2390 spectrophotometer. The infrared
spectra were recorded in the range 4000- I 80 cm·' with a
Perkin-Elmer 983 G spectrophotometer. The' H NMR
spectra were recorded on a Varian XL-300 MHz high
resolution instrument in CDCI) so lvent. The mass spec-
tra were recorded using Fan ning Mat 8230 mass spec-
trophotometer. The cyclic vo ltammetry was performed
with a BAS model CV-27 controller and a conventional
three electrode configuration with glassy carbon work-
ing electrode, silver/si lver chloride reference e lectrode
and platinum counter electrode. Nitrogen was used as a
purge gas and all solutions were prepared using 0. 1 M
tetrabutylammonium perchlorate (TBAP) supporting
electrolyte.
Results and Discussion
The analytical and IR data for all the ligands and
their cobalt(II) complexes are summarized in Table 1.
The 'H NMR spectra of BFMH, BFFH, BTMH and
BTEH in CDCI 3 show low field signals respectively at
11 .23,11.35,9.07,8 .91 ppm forthe imino proton present
in ligands. In the spectra of BFMH and BTMH, CH=N
peak is observed respectively at 8.60 and 8.80 ppm. Sig-
nals due to aromatic protons occurs as multiplets be-
tween 86.4 - 7.4 ppm. The resonance signal due to -
CH 3 protons present in BFEH and BTEH occur at 2.38
and 2.30 ppm respectively.
The mass spectra of BFMH, BFEH, BTMH and
BTEH show molecular ion peaks. The important peaks
observed in the mass spectra of these li gands are m/e 67,
77, 105, 125, 139 and 161 respectively corresponding to
C 4 H )O, C 6 H s ' C 6 H s CO, C 4 H 3 0(CH 3 )C : N-NH 2'
(BFEH), C4 H)S(CH))-C : N-NH2 (BTEH); C 6HsCONH ;
N-C-CH) (BTEH).
All the complexes are crystalline solids, stable at room
temperature, non-hygroscopic, soluble in chloroform,
DMF and DMSO, but insoluble in water, methanol and
264 iNDIAN J CHEM, SEC. A, MARCH 1999

Table 2 - Elec'ronic spectral data and ligand field parameters of cobalt complexes

Complex Method of v1 v2 v3 8 ova 8 35 b 10Dq v2 -v 1 v!v 1 LFSE

evaluation K-cal.
mole-I
[Co(BFMH)2 Ci 2J Observed 14705 18180
A 6692 143 52 17487 785 - 693 0.8 1 7668 7660 2.144 21.88
B Fitted! 14361 17488 815 ±692 0.84 7429 7669 2.146
C Fitted 14632 18045 854 - 135 0.88 8013 7940 2.186

[Co(BFE)2J Observed 15040 17543

A 6924 1483 1 17127 745 - 416 0.77 7904 7907 2.142 22.60
B Fitted 14002 17174 774 -1038 0.797 7480 7078 2.022
C Fitted 15218 17894 787 ± 351 0.8 10 81 16 8294 2. 197

[Co(BTMH)2 Ci 2J Observed 15387 17390

A 7185 15382 17384 746 - 16 0.768 8189 8197 2.140 23.42
B Fitted 15344 17355 745 - 45 0.767 8170 8159 2.135
C Fitted 15402 17424 748 ± 45 0.770 8202 8217 2. 143

[Co[BTE)2J Observed 15625 17240

A 7249 15480 16950 712 - 290 0.733 8230 8231 2. 130 23.51
B Fitted 14892 16975 732 - 733 0.753 7938 7643 2.054
C Fitted 14295 17476 241 ±1330 0.763 8376 7046 1.971

a Difference between observed and calculated value

b Ratio of free ion and the complex

~C /R fIl
~S~C
/ R

N
II IIN
""--NH ~NH

I I
50)J A
O=C'@ \
O=C

1_ R = H BFM H
"©
111_ R= H BTMH
II. R=CH3BFEH =
. IV _ R CH 3 BTEH

ethanol. The molar conductivities of -10- 3 M solution

of the complex in DMF were found in the range
n-
8-15 I cm- 2 mol -I indicating their non -e lectrolytic na-
ture l3 . The analytical data support the 1:2 (metal :ligand)
composition of the comp lexes . The magnetic moments
of cobalt(II) complexes of BFMH, BFEH, BTMH and
BTEH are respectively found to be 4.5, 4.0,4.3 and 4.5
BM suggesting a high spin octahedral geometry with a
0-7 0·9 1.1 1.3 1-5 1.7
very high orbital contribution attributable to the three-
- E/V
fold degeneracy of the 4T? (F) ground state term I4.15 .
-g
The electronic spectra of complexes were recorde d in
Fig. I - Cycli c voltammogram of [Co(BFMH)zJ in DMF in 0.1
M [TBAP] vs Ag/AgCl reference eleclfode (Scan rate DMF. Two distinct bands in the range 14705-15625 and
100 mY s-I ) , " 17242-18180 cm- I were observed in the electronic spec-
 RAO e/ al. : HEXACOORDIN ATION OF COBALT(II ) CO MPLEXES
Tab le 3 - Cyclic voltammetric data of cobalt co mpl exes in DMF co nt ainin g 0.1 M TB A I at glassy carbon electrode, temp. 25°C
Complex Cobalt
redox
co uple
Co(II )- BFMH 111/1/ -0.65
JIll -1 .435 -1.350
Co(II)-BFEH 11//1/ -0.54
JIll -1 .54 - 1.47
Co(II)-BTMH 111111 -0.73
JIll -1. 24
Co(lI)-BTEH I11111 -0 .62
1/11 -1 .36
tra of cobalt complexes (Table 2) attributable to th e
4T lg(F) ~ 4A 2g(F) (V 2 ) and 4T l g(F) .~ 4A Ig (P)(v 3 )
tran sition respectively in an octahedral fi eld . Important
li gand field parameters are presented in Tabl e 2. The
calculated values for Dq. B and B,,; li e in the same range
as that reported for octahedral cobalt(II) complexes. The
va lue of v I is calculated theoretica Il y l5,16 by u sin g th e
equation, VI = 5 Dq - 7.5 B + 1/2 (225 B2 + 100 Dq2
+ 180 Dq) I/2 .
The values of 10 Dq and Racah paramete rs of the
complexes were calculated u sing the observed v 2 and V3
values. The rati o of v? observed to v I calculated is found
to be in the range 1.97-2.19 as required for octahedral
coba lt(IT) co mpl exes l7. C o balt complexes with BFEH
and BTEH have hi g h 10 Dq valu es presumably due to
the high stability fac ilitated by hi g h denticity of these
li gand s.
Some important bands observed (Tabl e I) in the in-
frared spectra of BFMH, BFEH and BTE H , and the ir
co mplex es are considered for the ide ntifi cation o f don or
sites of the li gand s. The IR spectra of free li gand s ex-
hibit v(N-H) absorbance band s at c([.3250 and v (C=N)
band s ca. 1640 c m- I indicating th at the li gands ex ist in
keto form in the so lid state. However, in so luti on, the
li gands probably ex ist in equilibrium with tauto meric
enol form . By the loss of proton, the enoli c form may
act as a unin egat ive li gand . The band s appearin g in th e
spectra of li gand s - 1660, 1640, 1535, 1015 cm, l are
attributed 18 to amide I [v(C=O)] , v(C=N), amide U [~ ( N­
H ) + (C-N)] modes respecti ve ly. Th e two strong band s
o bserved at 7 10-690 and 610-605 cm,l reg ions 19.20 are
due to furan/thi oph e ne rin g de formation modes.
265
6.E (mY )
-1.39 85
-1.50 70
Cobalt complexes of BFMH and BTMH
The presence of v(N-H) in the spectra of these co m-
plexes suggest that FABH and TABH re main protonated
in chelation. The amide I and amide II bands shi ft to
lower frequencies in the spectra of these complexes. A
strong band observed in the spectra o f these li ga nds at
1640 cm, l is shifted to lower wave numbe r suggest ing
the participation of azomethine nitrogen in coOt'dina-
tion 21 On the other hand v (M-N) band is shifted to
higher frequ e nc ies 22 in the spec tra of both comp lex es
supporting th e coordination of azo methin e nitroge n
atom. Simila rl y, the hi g hest frequency ba nd observed
due to v(C=O) is shifted to lowe r wave numbe r sug-
gest in g the parti c ipation of carbo ny l oxygen in coordi-
nation. Th e non-li gand bands occurrin g in the region
500-585 ; 475-490 and 260-295 cm,l are tentati ve ly as-
s ig ned to v(M -O ), v (M-N) and v (M-CI ) vibrat io na l
modes respective ly23,
Cobalt complexes of BFEH and BTEH
B and s due to v (N-H ) and v(C=O) stretc hin g vibra-
tion s are no t observed in the IR spectra of these co m-
plexes. In stead, they show new bands charac teri st ic 24
o f v (NCO) in the spec tra o f these complexes. Th e ap-
pea rance of ~ (NCO) stre tc hing vibrat ion in the spect ra
of these cobalt co mpl exes suggests th e presence of
>C=N-N=C< res idues of the stoic hi ometry and th e de-
structi on of keto group presumabl y via enoli sati o n and
bondin g of the li gand throug h the res ultin g e nolate oxy-
gen. The red s hift of the rin g de formation vibrations in
the IR spectra of these comp lexes suggest th e parti c ipa-
 266 INDIAN J CHEM , SEC. A, MARCH 1999
v References
X=O or S
VI
ti on of furan oxygen and thi ophene sulphur in complex
formation. The bands observed in the 500-585 and 475-
490 e m-I reg ions which are absent in th e spect ra of
li gands may tentatively be assigned to v(M-O) and v(M-
N) modes respectively.
The cyclic voltammetri cs result s of compl exes are
summari zed in Table 3. Typica l cyc li c vo ltam mog ram
of coba lt complex of BFMH IS g iv e n In
F ig. I. The reduction of cobalt(H) to cobalt(l) depend s
on the ab ility of equatorial ligand to stabilize the cobalt(l)
ox idation state 25 . The cobalt complexes o f BFMH and
BFEH are reduced from cobalt(II) to coba lt(l) at EII2
va lues of -1 .39 and 1.50 V vs Ag-AgCI. These results
indi cate that the B FEH has greater ability to stabili ze
Co(!) oxidati on state. The EII2 va lues of present com-
plexes for Co(lII) ~ Co(II) and Co (II) ~ Co(!) are com-
parable to those cobinamides 26 . The absence of counter
oxidati on wave for Co(II) ~ Co(IlI) may be understood
in term s of increas in g difficulty to oxidize Co(H) in th e
form of co mplex and in non-aqu eous conditions.
Based on molar conductance, magnetic and spectral
data, octahedral structure (V, VI) is suggested for the
complexes. Our results suggest th at cobalt(lI) complexes
prefers to exist as octahedral structure irrespecti ve of
substitution and denticity of aroylhydrazones probabl y
to mimic the naturally occurring biomo lecul e viz. vita-
min B 12 •
Acknowledgement
We are thankful to the DST, New Delhi (Grant NO.SPI
S I IF-07/92), for financial support.
I Mesubi M, Adediran D & Ugo B, Synth React inorg IIwt -org
Cltem, 23 (1993) 435.
2 Mohan M, Kumar A, Kumar M & Jha N K, II/org chilli acta.
136 ( 1987) 65.
3 Ma T S & Tei n T M, Antibodies GI/d Chelll othemp.". 3 ( 1953)
491.
4 Bau-Hri . N P, Xuong M D, Binon F & Roger F, J chell/ Soc
( 1953) 1358.
5 Moon M W, Friedman A R & Sieinhard A, J Agr Food ClWIII ,
20 ( 1972) 11 87 and Cltem Abstr 105 ( 1986) 78839 .
6 Moon M W, Geomrich E G & Kauga rs G, J Ag r Food Chem,
20 ( 1972) 888.
7 Srivaslava R S, II/ org Chilll Acta , 56 (198 1) 65 and references
Iherein .
8 Dulla K L & Hussa in M M,.I sciel/tll/d Res, 44 ( 1985 ) 635.
9 Say,~ i Rao & Hussain Reddy, II/ dial/ J ChcIII , 35A ( 1996) 68 1.
10 Radhakrishna Reddy M, Mohana R ,~u K & Hu ssain Reddy K,
Indial/ J Chelll , 35A ( 1996) 677.
II Hussain Redd y K, Radhakrishna Reddy M & Mohan3 Raju K,
Polyhedrol/ , 16 ( 1997) 2679.
12 Radhakrishna Reddy M, Hu ssai n Rcdd y K & Mohan 3 Rajll K,
Polyhedrol/ , 17 ( 1998) 1355. _
13 Geary M J, Coo rd chem Rev, 7 (1971 ) XI.
14 COllon F A & Wilkinson G, Adl'al/ ced iI/organic cile//lis/l)'
(Jo hn Wiley, New York) 1988.
15 Singh M, Syl/tfl React inO/'R met org Chem, 16 ( 1986) 915.
16 Figgis B M, IlIIrodllction to ligal/d fields (Intersciencc, ew
York) 1960.
17 Lever A B P & Odgen P, J chelll Soc A, ( 1967) 204.
18 Rastogi D K & Sharma K C, J il/org lWei Cho l/ , 36 ( 1974)
2222.
19 Co lthup N B, Dal y L H & Wiberly S B, II/ frod llctiol/ to iI/Fa-
red and Ra//lal/ spectroscol')' (A cademic Press, New York )
1964, p. 237.
20 Ibrahim K M, Bill! Soc chilli F,:, 28 ( 1991) 327.
21 Agarwal K C & Nagang K K.II/ org chilli ACla, I (1973) 65 .
22 Roastzur M, Specfmchim Acta , 19 ( 1963) 1107 .
23 Nakamoto K, II/Fared al/d Ra//lal/ speClra 0/ inorgclllic and
coordination cOIllPounds. 3rd Edn (Wiley, New York). 1978.
24 Singh N K & Tripathi R. Trans Met Che//l . i 3 ( 1988) 346.
2S Costa G. PlIxeddu A & Tauzer G, In olS nucl che//l Le/{, 4,
(1968) 319.
26 Lippard S J (ed), Current research topics in iJlOillorganic che//l -
istl )' (John Wiley. New York ) 1973 , p 196.